Solid State Fluorination on the Minute Scale: Synthesis of WO[subscript 3;#8722;x]F[subscript x] with Photocatalytic Activity
Abstract not provided
Lange, Martin Alexander↗
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Pressure-driven density match nucleates metastable r8 phases from amorphous Si and Ge
The pressure–temperature phase behavior of covalent disordered solids such as amorphous silicon and germanium is complex. Questions remain on possible glass transitions, on polyamorphism via amorphous–amorphous transitions, on connections with liquid–liquid transitions, on structure-behavior relationships, and on their potential as precursor for novel methods for material discovery. Here we demonstrate experimentally the nucleation of a metastable, four-fold coordinated rhombohedral r8 phase from pure amorphous silicon and germanium upon room temperature compression at pressures below 10 GPa. Accompanying theory reveals a strong pressure-driven distortion of the bond angle transforming the starting tetrahedral low-density amorphous network to a distorted four-fold coordinated medium-density state. This state is of lower density than metallic high-density networks, resembles the crystalline r8 phase and initiates its nucleation. Our finding shows that polyamorphism is not the only possible transformation mode for these amorphous solids and that instead nucleation of interesting functional phases at potentially useful pressures is possible. Such novel access modes to metastable structures are critical for future exploitability and could be useful for other tetrahedral materials including carbon, where the related (bc8) post-diamond phase remains elusive. Our observed density match between an amorphous and a metastable crystalline phase clearly allows for a new phase transition pathway, while corresponding theory demonstrates how carefully validated atomistic simulations can guide prediction, discovery and synthesis of novel material structures.
Materials discovery↗
Activity-induced migration of viscous droplets on a solid substrate
Active matter exploits motion to induce changes in shape and conformation via external input. Here, in this paper, we establish theoretically that viscous liquid droplets containing magnetic nanoparticles with frozen-in magnetic moments, sitting on a solid substrate and surrounded by an ambient gas phase, can deform and migrate under the influence of a magnetic torque. The effect arises because the collective rotation of the magnetic nanoparticles at the liquid–gas interface tilts the droplet away from a symmetric configuration, breaks the reflection symmetry with respect to the centre axis, and leads to a left–right asymmetry of the contact angles. A sufficiently strong magnetic torque leads the contact angles to overcome hysteresis effects leading the droplet to migrate. We develop a general framework to explain how symmetry-breaking affects droplet migration. Thus previous results of droplet spreading and migration can be recovered as special cases. Such droplets can be employed as agents in active surfaces and can move against gravity, chemical and thermal gradients, providing a mechanism that could be utilized by both industry and medicine.
Aggarwal, A.↗
Kinetics of the Topochemical Transformation of (PbSe) m (TiSe 2 ) n (SnSe 2 ) m (TiSe 2 ) n to (Pb 0.5 Sn 0.5 Se) m (TiSe 2 ) n
Solid-state reaction kinetics on atomic length scales have not been heavily investigated due to the long times, high reaction temperatures, and small reaction volumes at interfaces in solid-state reactions. All of these conditions present significant analytical challenges in following reaction pathways. Herein we use in situ and ex situ X-ray diffraction, in situ X-ray reflectivity, high-angle annular dark field scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy to investigate the mechanistic pathways for the formation of a layered (Pb 0.5 Sn 0.5 Se) 1+δ (TiSe 2 ) m heterostructure, where m is the varying number of TiSe 2 layers in the repeating structure. Thin film precursors were vapor deposited as elemental-modulated layers into an artificial superlattice with Pb and Sn in independent layers, creating a repeating unit with twice the size of the final structure. At low temperatures, the precursor undergoes only a crystallization event to form an intermediate (SnSe 2 ) 1+γ (TiSe 2 ) m (PbSe) 1+δ (TiSe 2 ) m superstructure. At higher temperatures, this superstructure transforms into a (Pb 0.5 Sn 0.5 Se) 1+δ (TiSe 2 ) m alloyed structure. The rate of decay of superlattice reflections of the (SnSe 2 ) 1+γ (TiSe 2 ) m (PbSe) 1+δ (TiSe 2 ) m superstructure was used as the indicator of the progress of the reaction. Here, we show that increasing the number of TiSe 2 layers does not decrease the rate at which the SnSe 2 and PbSe layers alloy, suggesting that at these temperatures it is reduction of the SnSe 2 to SnSe and Se that is rate limiting in the formation of the alloy and not the associated diffusion of Sn and Pb through the TiSe 2 layers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Nontrivial strength of van der Waals epitaxial interaction in soft perovskites
The van der Waals (vdW) bond is traditionally believed to be orders of magnitude lower than the typical chemical bond (i.e., ionic, metallic, or covalent), and hence the effects caused by a vdW interface are thought to be trivial. In this work, by investigating the vdW epitaxial growth of a mechanically soft perovskite on the vdW substrate, we obtained the solid proof of strong non-negligible vdW interaction. The experimental results illustrate the formation of cracks and holes for the relaxation of the vdW strain as well as a lattice-constant-dependent epitaxial angle evolution and a pronounced band-structure change. The first-principles calculations indicate that the contribution of the vdW interaction energy at the epitaxial interface reaches up to more than a quarter of the overall interaction energy far exceeding the traditionally recognized vdW bonding strength. Both the experimental and the theoretical work show that given the appropriate material system, the vdW interaction could be strong enough to significantly manipulate material properties.
36 MATERIALS SCIENCE↗
Magnetic Weyl semimetal phase in a Kagomé crystal
Weyl semimetals are crystalline solids that host emergent relativistic Weyl fermions and have characteristic surface Fermi-arcs in their electronic structure. Weyl semimetals with broken time reversal symmetry are difficult to identify unambiguously. In this work, using angle-resolved photoemission spectroscopy, we visualized the electronic structure of the ferromagnetic crystal Co 3 Sn 2 S 2 and discovered its characteristic surface Fermi-arcs and linear bulk band dispersions across the Weyl points. Here, these results establish Co 3 Sn 2 S 2 as a magnetic Weyl semimetal that may serve as a platform for realizing phenomena such as chiral magnetic effects, unusually large anomalous Hall effect and quantum anomalous Hall effect.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Supersonic tests of an 0.015 scale space shuttle mated vehicle model (67-OTS) in the LaRC UPWT to obtain aerodynamic force data (IA42A/B)
Wind tunnel tests were conducted of the NASA/Rockwell 0.015 scale configuration 4 mated space shuttle vehicle. Data were obtained for a range of Mach numbers from 1.60 to 4.63 and angles of attack from minus 10 degrees to plus 10 degrees. A complete model build-up was performed. Longitudinal and lateral directional stability and control data were obtained for the tank alone, tank plus solid rocket boosters, and mated configuration of tank plus orbiter plus solid rocket boosters. Single component rudder hinge moment data were obtained at rudder deflections of zero degrees and minus 20 degrees for each Mach number tested.
Hardin, R.↗
Experimental study of the effectiveness of cylindrical plume simulators for predicting jet-on boattail drag at Mach numbers up to 1.30
An investigation has been conducted in a 16-foot transonic tunnel to determine the effectiveness of utilizing solid circular cylinders to simulate the jet exhaust plume for a series of eight nacelle-mounted isolated circular-arc afterbodies. This investigation was conducted at Mach numbers from 0.40 to 1.30 at an angle of attack of 0. Plume simulators with simulator diameter to nozzle-exit diameter ratios of 0.82, 0.88, 0.98, and 1.00 were investigated. Results of this investigation indicate that use of one of the larger diameter simulators at all Mach numbers would generally result in pressure-coefficient distributions and drag coefficients useful for preliminary design work.
Reubush, D. E.↗
Compact, Broadband Infrared Spectrometer
Large-aperture, wide-angle, broad-band infrared spectrometer compact and light in weight. Based on double-pass version of Schmidt optical system that acts as both collimator and camera. Because optical system contained in piece of solid glass, it is mechanically and thermally stable. System made of water-free fused silica to minimize absorption of infrared radiation. Although in principle made from single, solid piece, in practice made in two pieces cemented together. Fabrication easier and simpler if more cemented surfaces used so each optical surface grounded and polished like single lens element.
Page, Norman A.↗
Discovery of Graphene-Water Membrane Structure: Toward High-Quality Graphene Process
It is widely accepted that solid-state membranes are indispensable media for the graphene process, particularly transfer procedures. But these membranes inevitably bring contaminations and residues to the transferred graphene and consequently compromise the material quality. This study reports a newly observed free-standing graphene-water membrane structure, which replaces the conventional solid-state supporting media with liquid film to sustain the graphene integrity and continuity. Experimental observation, theoretical model, and molecular dynamics simulations consistently indicate that the high surface tension of pure water and its large contact angle with graphene are essential factors for forming such a membrane structure. More interestingly, water surface tension ensures the flatness of graphene layers and renders high transfer quality on many types of target substrates. This report enriches the understanding of the interactions on reduced dimensional material while rendering an alternative approach for scalable layered material processing with ensured quality for advanced manufacturing.
36 MATERIALS SCIENCE↗
Line tension induced character angle dependence of dislocation mobility in FCC alloys
Here, we explore the character angle dependence of dislocation-solute interactions in a face-centered cubic random Fe0.70Ni0.11Cr0.19 alloy through molecular dynamics (MD) simulations of dislocation mobility. Using the MD mobility data, we determine the phonon and thermally activated solute drag parameters which govern mobility for each dislocation character angle. The resulting parameter set indicates that, surprisingly, the solute energy barrier does not depend on character angle. Instead, only the zero-temperature flow stress—which is dictated by the activation area for thermal activation—is dependent on character angle. By analyzing the line roughness from MD simulations and the geometry of a bowing dislocation line undergoing thermal activation, we conclude that the character angle dependence of the activation area in this alloy is governed by the dislocation line tension, rather than the dislocation-solute interaction itself. Our findings motivate further investigation into the line geometry of dislocations in solid solutions.
36 MATERIALS SCIENCE↗
Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp 3 Centers
Tetracyanomethane, C(CN) 4 , is a tetrahedral molecule containing a central sp 3 carbon that is coordinated by reactive nitrile groups that could potentially transform to an extended CN network with a significant fraction of sp 3 carbon. High-purity C(CN) 4 was synthesized, and its physiochemical behavior was studied using in situ synchrotron angle-dispersive powder X-ray diffraction (PXRD) and Raman and infrared (IR) spectroscopies in a diamond anvil cell (DAC) up to 21 GPa. The pressure dependence of the fundamental vibrational modes associated with the molecular solid was determined, and some low-frequency Raman modes are reported for the first time. Crystalline molecular C(CN) 4 starts to polymerize above ~7 GPa and transforms into an interconnected disordered network, which is recoverable to ambient conditions. Lastly, the results demonstrate feasibility for the pressure-induced polymerization of molecules with premeditated functionality.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Inverse Temperature Dependence of Charge Carrier Hopping in Quantum Dot Solids
In semiconductors, increasing mobility with decreasing temperature is a signature of charge carrier transport through delocalized bands. We show that this behavior can also occur in nanocrystal solids due to temperature-dependent structural transformations. Using a combination of broadband infrared transient absorption spectroscopy and numerical modeling, we investigate the temperature-dependent charge transport properties of well-ordered PbS quantum dot (QD) solids. Contrary to expectations, we observe that the QD-to-QD charge tunneling rate increases with decreasing temperature, while simultaneously exhibiting thermally activated nearest-neighbor hopping behavior. Using synchrotron grazing-incidence small-angle X-ray scattering, we show that this trend is driven by a temperature-dependent reduction in nearest-neighbor separation that is quantitatively consistent with the measured tunneling rate.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of grain dissolution on sloping ground
The static and dynamic stability of natural or constructed slopes can be affected by dissolution or dissolution-like phenomena. Their underlying mechanisms, however, remain unclear. New experimental results and discrete element simulations provide particle-level and macroscale information on the consequences of mineral dissolution on slope behavior. At the microscale, load-carrying grain arches develop around dissolving particles, the porosity increases, and contact force chains evolve to form a honeycomb topology. At the macroscale, while vertical settlements are the prevailing deformation pattern, lateral granular movements that create mass wasting are prominent in sloping ground, even under the quasi-static granular loss. Horizontal grain displacement is maximum at the surface and decreases linearly with the distance from the slope surface to become zero at the bottom boundaries, much like vertical granular displacement along the depth. Sediments with smaller friction angles and steeper slopes experience greater displacement, both vertically and horizontally. Slopes become flatter after dissolution, with the reduction in slope angle directly related to the loss in ground elevation, ΔH/H o . Yet, because of the porous fabric that results from dissolution, vertical shortening is less than the upper bound, estimated from the loss in the solid mass fraction, ΔH/H o ≈SF. Under water-saturated conditions, the post-dissolution fabric may lead to sudden undrained shear and slope slide.
42 ENGINEERING↗
SU-F-T-319: The Impact of Radiation Beam Obliquity and Air Gap Thickness On Optically Stimulated Luminescent in Vivo Dosimetry for Radiation Therapy
Purpose: Optically-stimulated luminescent dosimeters (OSLDs) are increasingly utilized for in vivo dosimetry of complex radiation delivery techniques. Measured doses, however, underestimate planned doses for plans that utilize thermoplastic mask immobilization. The purpose of this work was to quantify the effect of beam obliquity and air gap span between the mask and backscatter material, on measured-to-planned OSLD dose agreement. Methods: A previously-used thermoplastic mask was cut, reheated, and flattened to form a 33 by 9 cm{sup 2} stage approximately 2 mm thick. Two OSLDs were placed on the stage on 5 cm of solid water, covered with 50 by 50 by 5 mm{sup 3} square of bolus, and scanned in the CT simulator. Plans were created with 10 by 10 cm{sup 2} open fields using 4, 6, 10, and 15 MV photon beams at 0°, 45°, and 90° incidence. The isocenter was placed between the OSLDs at 5 mm depth. Dose was calculated and averaged for two OSLDs. Artificial air gaps of 3, 5, 10, and 20 mm were introduced in the plan and dose was recalculated for each energy/angle/gap combination. The experimental setup was replicated on a linear accelerator and air gaps were introduced by “bridging” the thermoplastic stage across solid water plastic of varying thickness. Fields were delivered as planned. OSLDs were read 12–15 hours after irradiation. Results: Measured-toplanned percent differences were constant with increasing gap thickness for 0° and 45° beam angles. At 90° and 0 cm gap, planned dose underestimated measured dose by 10–23% for all energies. This discrepancy decreased linearly to 0% with a 20 mm gap. OSLD signal did not decrease more than 6% for any gap span and energy. Conclusion: With the exception of parallel beam incidence, beam obliquity and air gap thickness did not have a substantial effect on measured-to-planned dose agreement.
07 ISOTOPE AND RADIATION SOURCES↗
Compact and multi-view solid state neutral particle analyzer arrays on National Spherical Torus Experiment-Upgrade
A compact and multi-view Solid State Neutral Particle Analyzer (SSNPA) diagnostic based on silicon photodiode arrays has been successfully tested on the National Spherical Torus Experiment-Upgrade (NSTX-U). The SSNPA diagnostic provides spatially, temporally, and pitch-angle resolved measurements of fast-ion distribution by detecting fast neutral flux resulting from charge exchange (CX) reactions. The system consists of three 16-channel subsystems: t-SSNPA viewing the plasma mid-radius and neutral beam (NB) line #2 tangentially, r-SSNPA viewing the plasma core and NB line #1 radially and p-SSNPA with no intersection with any NB lines. Due to the setup geometry, the active CX signals of t-SSNPA and r-SSNPA are mainly sensitive to passing and trapped particles respectively. In addition, both t-SSNPA and r-SSNPA utilize three vertically stacked arrays with different filter thickness to obtain coarse energy information. The experimental data show that all channels are operational. The signal to noise ratio is typically larger than 10 and the main noise is x-ray induced signal. The active and passive CX signals are clearly observed on t-SSNPA and r-SSNPA during NB modulation. The SSNPA data also indicate significant losses of passing particles during sawteeth, while trapped particles are weakly affected. Fluctuations up to 120 kHz, have been observed on SSNPA, and they are strongly correlated with magnetohydrodynamics (MHD) instabilities.
Charge exchange neutral particle fast ion distribu↗
Technologies for Maintaining Animals in Space: Lighting, Air Quality, Noise, Food and Water
In the terrestrial environment multiple time cues exist. Zeitgebers have been identified and studied for their ability to convey temporal information to various physiological systems, In the microgravity experiment it is necessary to define time cues within the flight hardware prior to flight. During flight if changes in the Circadian System (e.g., mean, phase angle, period) occur this would indicate that the gravity vector is important relative to biological timing. This presentation is concerned with the environmental parameters to support rodent experiments in microgravity. The Animal Enclosure Module (AEM) provides solid food bars and water via lixits ad libitum. Flight animals (Sprague-Dawley rats, 60 - 300g) when compared to ground controls show similar growth (mean growth per day, g +/- SD; flight 5.4 +/- 2.0, ground 5.9 +/- 2.1). Current AEMs use incandescent lighting (approx. 5 Lux). Light emitting diode (LED) arrays are being developed that provide a similar light environment as cool-white fluorescent sources (40 Lux). In ground based tests (12L:12D), these arrays show normal circadian entrainment (Tau = 24.0) with respect to the behavioral responses. measured (drinking, eating, gross locomotor activity). A newly developed ultra high efficiency filter system can entrap all feces, urine and odors from 6 rats for 24 days. Maximum sound level exposure limits (per octave band 22 Hz - 179 kHz) have been established. The AEM will effectively support animal experiments in microgravity.
Winget, C. M.↗
Technologies For Maintaining Animals In Space: Lighting, Air Quality, Noise, Food And Water
In the terrestrial environment multiple time cues exist. Zeitgebers have been identified and studied for their ability to convey temporal information to various physiological systems. In the microgravity experiment it is necessary to define time cues within the flight hardware prior to flight. During flight if changes in the Circadian System (e.g., mean, phase angle, period) occur this would indicate that the gravity vector is important relative to biological timing. This presentation is concerned with the environmental parameter: to support rodent experiments in microgravity. The Animal Enclosure Module (AEM) provides solid food bars and water via lixits and ad libitum. Flight animals (Sprague-Dawley rats, 60 - 300g) when compared to ground controls show similar growth (mean growth per day g, plus or minus SD; flight 5.4 plus or minus 2.0, ground 5.9 plus or minus 2.1). Current AEMs use incandescent lighting (approx. 5 Lux). Light emitting diode (LED) arrays are being developed that provide a similar light environment as cool-white fluorescent sources (40 Lux). In ground based tests (12L:12D), these arrays show normal circadian entrainment (Tau = 24.0) with respect to the behavioral responses, measured (drinking, eating, gross locomotor activity). A newly developed ultra high efficiency filter system can entrap all feces, urine and odors from 6 rats for 24 days. Maximum sound level exposure limits (per octave band 22 Hz - 179 kHz) have been established. The AEM will effectively support animal experiments in microgravity.
Winget, C. M.↗